24700
2021
eng
doctoralthesis
1
2021-10-13
--
2021-10-04
Aggregation, Chirality and Reduction of Nonplanar Polycyclic Aromatic Hydrocarbons
Aggregation, Chiralität und Reduktion Nichtplanarer Polyzyklischer Aromatischer Kohlenwasserstoffe
Within this thesis the interactions between novel corannulene derivatives in solution as well as in the solid state by changing the imide residue of a literature known extended corannulene dicarboximide were investigated, in order to obtain a better understanding of the packing and possible charge transport in potential applications. Accordingly, the goal of the work was to synthesize and investigate an electron-poor corannulene bis(dicarboximide) based on previously published work but with higher solubility and less steric encumbrance in imide position to enable self-assembly in solution.
To obtain further insights into the conformational stability, structure and chiroptical properties of heavily twisted PBIs another aim of this thesis was the design, synthesis, and optoelectronic investigation of various fourfold directly arylated PBIs by substitution in bay position with smaller hydrocarbons with different steric demand, i.e., benzene, naphthalene and pyrene, which should be separable by chiral high performance liquid chromatography (HPLC).
As of yet, no concise study concerning the optical and electronic properties of differently core-substituted PBIs in the neutral as well as the mono- and dianionic state in solution is available, which also elucidates the origin of the different optical transitions observed in the absorption and emission spectra. Thus, in this thesis, the investigation of five PBI derivatives with different frontier energetic levels to produce a reference work of reduced PBIs was tackled.
Im Rahmen dieser Arbeit wurden die Wechselwirkungen zwischen neuartigen Corannulen-Derivaten sowohl in Lösung als auch im festen Zustand durch Veränderung des Imid-Restes eines literaturbekannten annulierten Corannulen-Dicarboximids untersucht, um ein besseres Verständnis der Packung und des möglichen Ladungstransports in potentiellen Anwendungen zu erhalten. Dementsprechend war es das Ziel der Arbeit, ein elektronenarmes Corannulenbis(dicarboximid) zu synthetisieren und zu untersuchen, das auf bereits veröffentlichten Arbeiten basiert, jedoch eine höhere Löslichkeit und weniger sterischen Anspruch in der Imidposition aufweist, um die Selbstorganisation in Lösung zu ermöglichen.
Um weitere Einblicke in die Konformationsstabilität, Struktur und chiroptischen Eigenschaften von stark verdrillten PBIs zu erhalten, war ein weiteres Ziel dieser Arbeit das Design, die Synthese und die optoelektronische Untersuchung verschiedener vierfach direkt arylierter PBIs durch Substitution in Bucht-Position mit kleineren Kohlenwasserstoffen mit unterschiedlichen sterischen Anforderungen, z.B. Phenyl, Naphthalin und Pyren, die durch chirale Hochleistungsflüssigkeitschromatographie (HPLC) trennbar sein sollten.
Bisher gibt es noch keine übersichtliche Studie über die optischen und elektronischen Eigenschaften von unterschiedlich kernsubstituierten PBIs im neutralen sowie mono- und dianionischen Zustand in Lösung, die auch den Ursprung der unterschiedlichen optischen Übergänge in den Absorptions- und Emissionsspektren aufklärt. In dieser Arbeit wurde daher die Untersuchung von fünf PBI-Derivaten mit unterschiedlichen energetischen Eigenschaften in Angriff genommen, um ein Referenzwerk reduzierter PBIs zu erstellen.
urn:nbn:de:bvb:20-opus-247000
10.25972/OPUS-24700
publish
X 129615
Deutsches Urheberrecht mit Print on Demand
Rebecca Renner
deu
swd
Corannulene
deu
swd
Polycyclische Aromaten
deu
swd
Perylenbisdicarboximide <Perylen-3,4:9,10-bis(dicarboximide)>
eng
uncontrolled
Aggregation
eng
uncontrolled
Chirality
eng
uncontrolled
Reduction
deu
uncontrolled
Perylenbisdicarboximide
deu
uncontrolled
Supramolekulare Chemie
Organische Chemie
open_access
Institut für Organische Chemie
Universität Würzburg
Universität Würzburg
https://opus.bibliothek.uni-wuerzburg.de/files/24700/Renner_Rebecca_NonplanarPAHs.pdf
29909
2020
2020
eng
229–234
3
2
article
1
2023-01-10
2020-09-09
--
Bowl-shaped naphthalimide-annulated corannulene as nonfullerene acceptor in organic solar cells
An electron-poor bowl-shaped naphthalimide-annulated corannulene with branched alkyl residues in the imide position was synthesized by a palladium-catalyzed cross-coupling annulation sequence. This dipolar compound exhibits strong absorption in the visible range along with a low-lying LUMO level at –3.85 eV, enabling n-type charge transport in organic thin-film transistors. Furthermore, we processed inverted bulk-heterojunction solar cells in combination with the two donor polymers PCE–10 and PM6 to achieve open-circuit voltages up to 1.04 V. By using a blend of the self-assembled naphthalimide-annulated corannulene and PCE–10, we were able to obtain a power conversion efficiency of up to 2.1%, which is to the best of our knowledge the highest reported value for a corannulene-based organic solar cell to date.
Organic Materials
2625-1825
10.1055/s-0040-1714283
https://www.thieme-connect.com/products/ejournals/html/10.1055/s-0040-1714283
urn:nbn:de:bvb:20-opus-299095
publish
Organic Materials (2020) 2:3, 229–234. doi:10.1055/s-0040-1714283
true
true
CC BY-NC-ND: Creative-Commons-Lizenz: Namensnennung, Nicht kommerziell, Keine Bearbeitungen 4.0 International
Kaan Menekse
Rebecca Renner
Bernhard Mahlmeister
Matthias Stolte
Frank Würthner
deu
uncontrolled
Chemie
eng
uncontrolled
corannulene
eng
uncontrolled
nonfullerene acceptors
eng
uncontrolled
curved π-systems
eng
uncontrolled
bulk-heterojunction solar cells
eng
uncontrolled
aggregation
Organische Chemie
open_access
Institut für Organische Chemie
Universität Würzburg
https://opus.bibliothek.uni-wuerzburg.de/files/29909/menekse_kaan_corannulene.pdf
20439
2020
eng
32-39
1
9
article
1
2020-05-18
--
--
Self-Assembly of bowl-shaped naphthalimide-annulated
corannulene
The self-assembly of a bowl-shaped naphthalimide-annulated corannulene of high solubility has been studied in a variety of solvents by NMR and UV/Vis spectroscopy. Evaluation by the anti-cooperative K\(_2\)-K model revealed the formation of supramolecular dimers of outstanding thermodynamic stability. Further structural proof for the almost exclusive formation of dimers over extended aggregates is demonstrated by atomic force microscopy (AFM) and diffusion ordered spectroscopy (DOSY) measurements as well as by theoretical calculations. Thus, herein we present the first report of a supramolecular dimer of an annulated corannulene derivative in solution and discuss its extraordinarily high thermodynamic stability with association constants up to > 10\(^6\)M\(^-\) \(^1\) in methylcyclohexane, which is comparable to the association constants given for planar phthalocyanine and perylene bisimide dyes.
ChemistryOpen
10.1002/open.201900291
urn:nbn:de:bvb:20-opus-204396
ChemistryOpen (2019) 9:1, 32-39. https://doi.org/10.1002/open.201900291
CC BY-NC-ND: Creative-Commons-Lizenz: Namensnennung, Nicht kommerziell, Keine Bearbeitungen 4.0 International
Rebecca Renner
Matthias Stolte
Frank Würthner
eng
uncontrolled
corannulene
eng
uncontrolled
π-π-interactions
eng
uncontrolled
aelf-assembly
eng
uncontrolled
aggregation
eng
uncontrolled
supramolecular chemistry
Organische Chemie
open_access
Institut für Organische Chemie
Förderzeitraum 2019
Universität Würzburg
https://opus.bibliothek.uni-wuerzburg.de/files/20439/Renner_ChemistryOpen_2020.pdf
24907
2021
eng
11997
12006
10
46
27
article
1
2021-11-11
2021-06-16
--
Chiral Perylene Bisimide Dyes by Interlocked Arene Substituents in the Bay Area
A series of perylene bisimide (PBI) dyes bearing various aryl substituents in 1,6,7,12 bay positions has been synthesized by Suzuki cross-coupling reaction. These molecules exhibit an exceptionally large and conformationally fixed twist angle of the PBI π-core due to the high steric congestion imparted by the aryl substituents in bay positions. Single crystal X-ray analyses of phenyl-, naphthyl- and pyrenyl-functionalized PBIs reveal interlocked π-π-stacking motifs, leading to conformational chirality and the possibility for the isolation of enantiopure atropoisomers by semipreparative HPLC. The interlocked arrangement endows these molecules with substantial racemization barriers of about 120 kJ mol\(^{−1}\) for the tetraphenyl- and tetra-2-naphthyl-substituted derivatives, which is among the highest racemization barriers for axially chiral PBIs. Variable temperature NMR studies reveal the presence of a multitude of up to fourteen conformational isomers in solution that are interconverted via smaller activation barriers of about 65 kJ mol\(^{−1}\). The redox and optical properties of these core-twisted PBIs have been characterized by cyclic voltammetry, UV/Vis/NIR and fluorescence spectroscopy and their respective atropo-enantiomers were further characterized by circular dichroism (CD) and circular polarized luminescence (CPL) spectroscopy.
Chemistry - A European Journal
10.1002/chem.202101877
urn:nbn:de:bvb:20-opus-249070
Chemistry - A European Journal 2021, 27 (46) 11997-12006. https://doi.org/10.1002/chem.202101877
false
true
CC BY: Creative-Commons-Lizenz: Namensnennung 4.0 International
Rebecca Renner
Bernhard Mahlmeister
Olga Anhalt
Matthias Stolte
Frank Würthner
eng
uncontrolled
Suzuki coupling
eng
uncontrolled
perylenebisimide dyes
eng
uncontrolled
circular polarized luminescence
eng
uncontrolled
chirality
Organische Chemie
open_access
Institut für Organische Chemie
Universität Würzburg
https://opus.bibliothek.uni-wuerzburg.de/files/24907/chem.202101877.pdf